Process for conditioning petroleum oils



Patented cc. 8, 11931 entree stares MELVIN DE GBOOTE, 10F ST. LUUIS, AND LOUIS T. MONSON, 0F LEWOOD, MSSOURI,

ASSIGNORS, BY MESNE ASSIGTS,

1'0 TRETOLITE CQMP, OF WEBST GROVES, MISSOURI, A CORPORATION OF MISSOURI PROCESS FOR CONDITIONING PETROLEUM OILS No Drawing. Application filed. March 3,

This invention relates to a process for conditioning petroleum oils of the kind in which water or brine, either in a free state or in an emulsified 'state, is combined with the oil. The process is applicable to petroleum oils that contain waterwhich can be removed or separated from the oil by a settling operation or by heating the oil, and the process is also applicable to petroleum oils of the kind commonly referred to as cut oil, roily oil,

emulsified oil and bottom settlings, which require treatment with a chemical demulsifying agent, electrical dehydrator or similar medium to dehydrate the oil and make it suitable for commercial use or to satisfy'commercia-l requirements.

We do not contend that our process will of itself break or resolve petroleum emulsions of the water and oil type, in which fine droplets of naturally-occurring,Waters or brines are dispersed in a more or lesslipermanent state throughout the oil constituting the continuous phase of the emulsion, but our process will materially assist in the breaking or resolution of such petroleum oils by processes, apparatus or procedure of the kind now commonly employed for this purpose. Due to the low cost of our process it is commercially feasible or practicable to use our process in conjunction with processes or apparatus of the kind employed to dehydrate petroleum emulsions, and it is also adaptable for use as a preliminary step or conditioning step in the treatment of petroleum oils that contain water which can be separated or removed with minimum trouble and expenseand without resorting to the use of demulsifying agents, electrical dehydrators or the like.

Briefly described, our process consists in subjecting petroleum oil containing water or brine, either in a free state or emulsified state, to theaction of a conditioning agent that contains, comprises or is composed of a substance which we will hereinafter refer to as sulfur dioxide extract, so as to assist in the action of subsequent procedure that is employed to effect the removal of such water or brine, which subsequent procedure may consist simply of settling the oil or heating the oil, or treating the oil with a chemical de- 1930. serial Ho. 432,975.

mulsifying agent or passing it through an electrical dehydrator, as is necessary in the dehydration of cut oil, roily oil and similar pe- I troduced into an oil line through which oil is flowing, or introduced into a tank in which the oil is stored. It is only necessary to use a very minute quantity of the conditioning agent, and in practicing our process, the amount of conditioning agent that is required will vary according to-the nature or characteristics of the particular oil being conditioned. As a typical example of our process, we will say that when the conditioning agent is used in a concentration of about 1 part of agent to 1,000 parts of oil being treated, the action of the subse uent treating procedure that is employed to or brine from the oil will be greatly enhanced or improved. At other times as little as 1 part of agent to 5,000 parts of oil may be sufficient. t

The sulfur dioxide extract contemplated by our process is an oil-soluble substance, and it is obtained or produced from petroleum distillates or other suitable hydrocarbon bodies, by means of liquid sulfur dioxide. One source of sup ly of such material is a by-product or resi 'uum obtained in the operation of purifying petroleum distillates by the well known Edeleanu process, described in U. S. PatentNo.911,553,toLazarEdeleanu, dated February 2, 1909. Said Edeleanu process, briefly described, consists in agitatingpetroleum distillate with liquid sulfur dioxide at a low temperature, and then permitting the mass to separate into two layers, the lower of which is a solution of aromatic e ect the removal of water and unsaturated compounds inli uid sulfur dioxide. The said solution may a so contain any sulfur-containing compounds originally pre ent in the petroleum distillate. After wit drawing the said solution fromthe reacice tion vessel, the sulfur dioxide is recovered by driving it off at a higher temperature, leaving a residuum which we will refer to as a sulfur dioxide extract. The sulfur dioxide may be re-cycled for further use in the process.

The sulfur dioxide extract, which appears as a residuum, consists of a mixture of compounds which contains only a trace of sulfur dioxide, and it is the sulfur dioxide extract that we prefer to use in practising our process. It contains chiefly aromatic bodies and unsaturated bodies. Some of the aromatics may be mono-cyclic and some polycyclic. Some may be hydrogenated aromatics. The unsaturated bodies may be of the aliphatic or of the cyclic series. In an average sample of residuum or sulfur dioxide extract of the kind above referred to, it is probable that all of these various types are present in larger or smaller quantities, although specific samples would vary in the percentage of each constituent present. For example, if Borneo petroleum distillate were subjected to treatment by the Edeleanu process, the residuum, or sulfur dioxide extract obtained would be expected to consist largely of aromatic bodies, whereas, if West Texas petroleum distillate were subjected to treatment b the Edeleanu process, the residuum, or sul ur dioxide extract obtained, would contain a smaller proportion of aromatics.

While we prefer, in practising our process, to use a conditioning agent that comprises, contains, or is composed of sulfur dioxide extract obtained'as a by-product in the purification of petroleumdistillate by the Edeleanu process, due to the low cost of such sulfur dioxide extract, we wish it to be understood that it is immaterial, so far as our invention is concerned, how or from what source the sulfur dioxide extract is obtained. We have ob tained good results with a conditioning agent composed of sulfur dioxide extract obtained in the purification of a distillate obtained from West Texas,crude petroleum by the useof liquid sulfur dioxide at a low temperature. M

Approximately 10% of the sulfur dioxide extract could be distilled at a temperature range of 360 F. to 390 F., and as the temperature was increased, the percentage of the sulfur dioxide extract distilled increased in about the following ratio, i. e:

Per cent 390400 F 11-20 4:01-410 F 21 -30 411421 F 31-40 422-430 F; 41*50 431-4455 F 51-60 4444.5? F 61-70 456-472 F 71-80 4:73-490 F 81-90 Above 490 F Sir-100.

The specific gravity of the sulfur dioxide extract obtained was approximately 0.899 at F. It contained onl a trace of bodies extractable by means 0 sodium hydroxide. Strong sulfuric acid dissolved a ortion of it with the evolution of heat. leum acted more vigorously, but in a similar fashion. The solution constituting the lower acid layer of the reaction mass contained sulfonic acids or similar bodies soluble in water. By means of 25% by volume of 66 Baum sulfuric acid, 11% of the sample was dissolved. Since no exact analysis of the material can be made to determine the amount of each member of the various homologous series present, no more complete characterization of the material can be given.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A process for conditioning petroleum oil that requires treatment to effect the removal of brine or water from same, which consists in subjecting the oil, prior to such treatment, to the action of a soluble conditioning agent, comprising a mixture of aromatic and unsaturated petroleum bodies extracted from petroleum by means of liquid sulfur dioxide.

2. A process for conditioning petroleum oil that requires treatment to effect the removal of brine or water from same, which consists in subjecting the oil, prior to such treatment, to the action of a minute quantity of a soluble conditioning agent, comprising sulfur dioxide extract of the Edeleanu purifying process.

3. A process for conditioning petroleum oil that requires treatment to effect the removal of brine or water from same, which consists proximately 0.899 at 60 F. and a boiling range of 360 F. to over 490 F.

MELVIN DE GROOTE. LOUIS T. MONSON. 

